Asymmetric hydrogenation catalysts and processes

A method for catalytic hydrogenation which comprises the steps of:

• (a) providing a Ru(II) catalyst of formula:
• 26
• or of formula:
• 27
• wherein:
• X is a heteroatom;
• L″, independent of other L″, is an optionally substituted hydrocarbyl group;
• M, independent of other M, is an electrophilic metal atom or cation;
• L′, independent of other L′ is a ligand selected from a solvent molecule, a halogen, an optionally substituted alkoxide, an optionally substituted aryloxide, an anionic ligand containing one or more halogen, one or more oxygen, or one or more nitrogen atoms or a ligand containing one or more oxygen, one or more nitrogen, one or more phosphorous atoms or a combination of oxygen, nitrogen or phosphorous atoms;
• Ru is a ruthenium atom in the +2 oxidation state;
• L is a ligand selected from a halogen, a solvent molecule, dihydrogen, a ligand containing one or more oxygen, nitrogen, and/or phosphorus chelating atoms, a π-bonded optionally substituted arene, a ligand containing one or more oxygen, one or more nitrogen or one or more phosphorous atoms in combination, and an X-L″p group, any two or more of L, L′ or L″ can be linked to form a ring and any of L, L′ or L″ can be chiral;
• and the integers n, m and p are the number of ligands L, L′ and L″, respectively, and range generally from 0 to 6 dependent upon the valency of the ligands, X, and M;
• and
• b) contacting a compound to be hydrogenated with the catalyst in the presence of a hydride source to thereby hydrogenate the compound.

A hydrogenation catalyst) catalyst of formula:

• 28
• or of formula:
• 29
• wherein:
• X is a heteroatom;
• L″, independent of other L″, is an optionally substituted hydrocarbyl group;
• M, independent of other M, is an electrophilic metal atom or cation;
• L′, independent of other L′ is a ligand selected from a solvent molecule, a halogen, an optionally substituted alkoxide, an optionally substituted aryloxide, an anionic ligand containing one or more halogen, one or more oxygen, or one or more nitrogen atoms or a ligand containing one or more oxygen, one or more nitrogen, one or more phosphorous atoms or a combination of oxygen, nitrogen or phosphorous atoms;
• Ru is a ruthenium atom in the +2 oxidation state;
• L is a ligand selected from a halogen, a solvent molecule, dihydrogen, a ligand containing one or more oxygen, nitrogen, and/or phosphorus chelating atoms, a n-bonded optionally substituted arene, a ligand containing one or more oxygen, one or more nitrogen or one or more phosphorous atoms in combination, and an X-L″P group, any two or more of L, L′ or L″ can be linked to form a ring and any of L, L′ or L″ can be chiral;
• and the integers n, m and p are the number of ligands L, L′ and L″, respectively, and range generally from 0 to 6 dependent upon the valency of the ligands, X, and M;
• or of formula:

A method for catalytic hydrogenation of a compound which comprises the steps of:

• (a) combining a first component containing the Ru (II) complex structure:
• 30
• wherein:
• X is a hetero atom;
• L″, independent of other L″, is an optionally substituted hydrocarbyl group;
• Ru is a ruthenium atom in the +2 oxidation state;
• L is a ligand selected from a halogen, a solvent molecule, dihydrogen, a ligand containing one or more oxygen, nitrogen, and/or phosphorus chelating atoms, a π-bonded optionally substituted arene, a ligand containing one or more oxygen, one or more nitrogen or one or more phosphorous atoms in combination, and an X-L″p group, any two or more of L, or L″ can be linked to form a ring and any of L, or L″ can be chiral;
• and the integers n, and p are the number of ligands L, and L″, respectively, and range generally from 0 to 6 dependent upon the valency of the ligands, and X,
• with more than one equivalent with respect to the Ru(II) complex of a second component that is a Lewis acid;
• and
• (b) contacting a compound to be hydrogenated with the combination in the presence of a hydride source to thereby hydrogenate the compound.

A method for hydrogenating a compound which comprises the steps of:

• (a) combining a first component containing the Ru(II) complex structure:
• 31
• wherein:
• X is a heteroatom;
• L″, independent of other L″, is an optionally substituted hydrocarbyl group;
• X′ is a good leaving group;
• Ru is a ruthenium atom in the +2 oxidation state;
• L is a ligand selected from a halogen, a solvent molecule, dihydrogen, a ligand containing one or more oxygen, nitrogen, and/or phosphorus chelating atoms, a π-bonded optionally substituted arene, a ligand containing one or more oxygen, one or more nitrogen or one or more phosphorous atoms in combination, and an X-L″p group, any two or more of L, or L″ can be linked to form a ring and any of L, or L″ can be chiral;
• and the integers n, and p are the number of ligands L, and L″, respectively, and range generally from 0 to 6 dependent upon the valency of the ligands, X′ and X,
• with one or more equivalents with respect to the Ru(II) complex of a second component which is a base and with more than one equivalent with respect to the base of a third component that is a Lewis acid and contacting the combination with a hydride source and the compound to be hydrogenated to thereby hydrogenate the compound.

A catalytic formulation which is prepared by combining a Ru(II) complex of formula:

• Ln—Ru—[—X—L″p]n′
• wherein:
• X is a heteroatom;
• L″ is an optionally substituted hydrocarbyl group;
• p is an integer dependent upon the valency of X and L″;
• L, independent of other L in the complex, is a ligand selected from a halogen, a solvent molecule, a ligand containing one or more oxygen, nitrogen or phosphorous chelating atoms, an arene and dihydrogen;
• and
• n and n′ are integers with n′ ranging from 1 to 6 and n ranging from 0 to 5 dependent upon the valency of L ligands and the value of n′;
• with at least one equivalent with respect to the Ru complex of a base and more than one equivalent with respect to the base of a Lewis acid.

A catalytic formulation which is prepared by combining a first component containing the Ru(II) complex structure:

• 34
• wherein:
• X is a heteroatom;
• L″, independent of other L″, is an optionally substituted hydrocarbyl group;
• X′ is a good leaving group;
• Ru is a ruthenium atom in the +2 oxidation state;
• L is a ligand selected from a halogen, a solvent molecule, dihydrogen, a ligand containing one or more oxygen, nitrogen, and/or phosphorus chelating atoms, a π-bonded optionally substituted arene, a ligand containing one or more oxygen, one or more nitrogen or one or more phosphorous atoms in combination, and an X-L″p group, any two or more of L, or L″ can be linked to form a ring and any of L, or L″ can be chiral;
• and the integers n, and p are the number of ligands L, and L″, respectively, and range generally from 0 to 6 dependent upon the valency of the ligands, X′ and X,
• with one or more equivalents with respect to the Ru(II) complex of a second component which is a base and with more than one equivalent with respect to the base of a third component that is a Lewis acid.

A catalytic formulation prepared by combining

• (a) a first component containing A method for catalytic hydrogenation of a compound which comprises the steps of:
• (a) combining a first component containing the Ru (II) complex structure:
• 35
• wherein:
• X is a heteroatom;
• L″, independent of other L″, is an optionally substituted hydrocarbyl group;
• Ru is a ruthenium atom in the +2 oxidation state;
• L is a ligand selected from a halogen, a solvent molecule, dihydrogen, a ligand containing one or more oxygen, nitrogen, and/or phosphorus chelating atoms, a π-bonded optionally substituted arene, a ligand containing one or more oxygen, one or more nitrogen or one or more phosphorous atoms in combination, and an X-L″P group, any two or more of L, or L″ can be linked to form a ring and any of L, or L″ can be chiral;
• and the integers n, and p are the number of ligands L, and L″, respectively, and range generally from 0 to 6 dependent upon the valency of the ligands, and X,
• with more than one equivalent with respect to the Ru(II) complex of a second component that is a Lewis acid.

A Ru(II) complex having the formula:

• 36
• wherein R, independent of other R in the complex, can be hydrogen, an optionally substituted alkyl group or an optionally substituted aryl group;
• R′, independent of other R″ in the complex, can be an optionally substituted hydrocarbyl group, R″, independent of other R″ in the complex, can be a hydrogen or an optionally substituted hydrocarbyl group;
• and R5, independent of other R5 in the complex , can be an optionally substituted hydrocarbyl group wherein any two or more of R, R′, R″ or R5 can be linked to form a ring.